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Highly oxygenated organic molecules (HOM) formed by the autoxidation of α-pinene initiated by OH radicals play an important role in new particle formation. It is believed that the accretion products, ROOR´, formed by the self- and cross-reaction of peroxy radicals (RO

Polycyclic Aromatic Hydrocarbon (PAHs) presents one of the most abundant class of environmental pollutants. Recent study shows a lab-synthesized PAHs derivative, helicenium, can selectively kill cancer cells rather than normal cells, calling for the in-depth understanding of the metabolic process. However, the origin of metabolites diversity and selectivity of P450 catalyzed PAHs metabolic activation is still unclear to a great extent. Here we systematically investigated P450 enzymes catalyzed activation mechanism of a representative PAHs, benzo[a]pyrene (BaP), and found the corresponding activation process mainly involves two elementary steps: electrophilic addition and epoxidation. Electrophilic addition step is evidenced to be rate determining step. Two representative binding modes of BaP with P450 were found, which enables the electrophilic addition of Heme (FeO) to almost all the carbons of BaP. This electrophilic addition was proposed to be accelerated by the P450 enzyme environment when compared with the gas phase and water solvent. To dig deeper on the origin of metabolites diversity, we built several linear regression models to explore the structural-energy relationships. The selectivity was eventually attributed to the integrated effects of structural (e.g. O-C distance and O-C-Fe angle) and electrostatic parameters (e.g. charge of C and O) from both BaP and P450.

The reactions of Criegee intermediates (CIs) play an important role in the formation of secondary organic aerosols that have negative effect on visibility, human health, and global climate. New particle formation (NPF) can contribute to more than half of the aerosols in terms of their number concentration. Here, the reactions of CIs with formamide (FA) in the gas-phase and at the air/water interface were investigated using quantum chemistry calculation and Born-Oppenheimer molecular dynamic simulations. The results show that the reaction mechanism of CIs with FA is similar to that with formic acid, and the formation of hydroperoxymethyl formimidate (P4) is the most favorable pathway both in the gas-phase and at the air/water interface. Moreover, the potential contribution of the products to NPF was also evaluated by means of the molecular dynamic simulations. The results indicate that the product (P4) can participate in the SA-based NPF and water molecules are beneficial to enhance the NPF. The exploration will provide insight into the reaction of CIs with amide and the effect of the Criegee chemistry on the atmospheric aerosols.

Despite increasing environmental concerns on ever-lasting Polyethylene Terephthalate (PET), its global production is continuously growing. Effective strategies that can completely remove PET from environment are urgently desired. Here biotransformation processes of PET by one of the most effective enzymes, leaf-branch compost cutinase (LCC), were systematically explored with Molecular Dynamics and Quantum Mechanics/Molecular Mechanics approaches. We found that four concerted steps are required to complete the whole catalytic cycle. The last concerted step, deacylation, was determined as the rate-determining step with Boltzmann-weighted average barrier of 13.6 kcal/mol and arithmetic average of 16.1 ± 2.9 kcal/mol. Interestingly, unprecedented fluctuations of hydrogen bond length during LCC catalyzed transformation process toward PET were found. This fluctuation was also observed in enzyme IsPETase, indicating that it may widely exist in other catalytic triad (Ser-His-Asp) containing enzymes as well. In addition, possible features (bond, angle, dihedral angle and charge) that influence the catalytic reaction were identified and correlations between activation energies and key features were established. Our results present new insights into catalytic mechanism of hydrolases and shed light on the efficient recycling of the ever-lasting PET.

Massively used plastics have caused worldwide environmental concerns. Polyesters like polylactic acid (PLA) are one of the mostly used plastics due to its excellent physical and chemical properties and low-cost advantages. It is critical to develop the elimination and recycle techniques for polyesters. Experimental studies have shown that a hydrolase RPA1511 isolated from Rhodopseudomonas palustris can efficiently depolymerize polylactic acid (PLA) into oligomers and monomers. It was also active against emulsified aliphatic polymers as well as multipurpose soluble ester monomers (α-naphthyl ester and p-nitrophenyl ester). In the present study, molecular dynamics simulations and molecular mechanics Poisson-Boltzmann surface area method were applied to screen all amino acids from hydrolase RPA1511 and identify the most important amino acids during substrate binding. Seven substrates were considered: PLA (dimer and tetramer), polycaprolactone, butylene succinate, 1-naphthyl acetate, 2-naphthyl formate, p-nitrophenyl acetate. The results highlighted the importance of amino acids like Tyr139, Tyr213, Arg259, Thr46. Subsequent quantum mechanics/molecular mechanics calculations were also performed to determine the detailed degradation mechanism of hydrolase RPA1511 toward PLA and explore the role of the active site residues during catalysis. The results demonstrated that degradation involves two elementary steps: enzyme acylation and PLA hydrolysis. The corresponding Boltzmann average barriers are 20.40 kcal/mol and 14.45 kcal/mol. The electrostatic influence analysis of 15 amino acids on the rate-determining step indicated that amino acids His114, Trp219 and Ala273 facilitate the reaction while the Arg244 suppresses the reaction which may serve as future mutation studies to enhance the enzymatic efficiency.

The various applications of iron oxide nanoparticles (NPs) in clinical care and wastewater treatment are rapidly developing, thus their biological safety is worth attention. The electrostatic interaction between cell membranes and NPs is the key mechanism behind membrane damage and membrane penetration. Cell membranes are generally negatively charged with a few positively charged domains. The role of the positively charged sites in the NP-membrane interaction needs further investigation. In this study, the ratio of the positively charged sites was adjusted in two model cell membranes: giant and small unilamellar vesicles (GUVs and SUVs). After exposure to negatively charged γ-Fe2O3 NPs, the adhesion of NPs on the membranes and the induced membrane disruption were studied by microscopic observation and quartz crystal microbalance (QCM) monitoring. γ-Fe2O3 NPs adhered to and disrupted the membranes containing even few positively charged sites, although the whole membrane exhibited a negative zeta potential and hence electrostatically repels the NPs. The number of adhered γ-Fe2O3 NPs increased remarkably on membranes with overall positive zeta potential, but more serious disruption happened to membranes with higher ratios of positively charged sites. Therefore, the membrane rupture was more correlated to the number of positively charged sites than to the zeta potential of the whole membrane. In addition, exposure to γ-Fe2O3 NPs decreased the order of the lipid molecules and hence increased the fluidity of the membrane phase, and the most significant phase change occurred in the negatively charged membrane with the highest ratio of positively charged sites. Infrared spectra indicated that γ-Fe2O3 NPs probably interact with the membranes via the phosphodiester and trimethylamine groups in the lipid head groups. Our research furthers our knowledge of the electrostatic interaction between NPs and cell membranes, which should help to predict the biological effects of γ-Fe2O3 NPs.

As an effective organochlorine pesticide, Dicofol has been extensively applied in more than 30 countries for protecting over 60 different crops. Considering its large consumption and potential adverse effect on human health (endocrine disrupting and carcinogenicity), the fate of Dicofol sprayed into the air is of public concern. In this study, we conducted a comprehensive study on the reaction mechanisms of p,p'-Dicofol with OH and NO3 radicals using DFT method. Comparing the abstrations by OH and NO3 radical, OH and NO3 radical addition reactions are predominant due to the lower potential barriers and stronger heat release. The phenolic substances (P1 P5), epoxides (P11 and P15), dialdehyde (P13) and other species (P8, P9, P10 and P14) are generated by OH additions and their subsequent reactions while OH abstraction reactions produce DCBP, P7 and chlorphenyl radical. Particularly, NO3 additions and their subsequent reactions yield dialdehydes (P16 and P17) and 2,8-DCDD, which is the first report of the generation of dioxin from atmospheric oxidation of p,p'-Dicofol. Additionally, based on the structure optimization and energy calculation, rate constants and Arrhenius formulas of the elementary reactions of p,p'-Dicofol with OH and NO3 radicals were obtained over the temperature range of 280–380 K and at 1 atm. The rate constants for the reactions of p,p'-Dicofol with OH and NO3 radicals are 1.51 × 10−12 and 8.88 × 10−14 cm3 molecule−1 s−1, respectively. The lifetime (τTotal) of p,p'-Dicofol determined by the reactions of OH and NO3 radical is 5.86 h, indicating a potential long-range transport in the atmosphere.

Recent studies have shown that surface ozone (O3) concentrations over central eastern China (CEC) have increased significantly during the past decade. We quantified the effects of changes in meteorological conditions and O3 precursor emissions on surface O3 levels over CEC between July 2003 and July 2015 using the GEOS-Chem model. The simulated monthly mean maximum daily 8 h average O3 concentration (MDA8 O3) in July increased by approximately 13.6 %, from 65.5±7.9 ppbv (2003) to 74.4±8.7 ppbv (2015), comparable to the observed results. The change in meteorology led to an increase in MDA8 O3 of 5.8±3.9 ppbv over the central part of CEC, in contrast to a decrease of about -0.8±3.5 ppbv over the eastern part of the region. In comparison, the MDA8 O3 over the central and eastern parts of CEC increased by 3.5±1.4 and 5.6±1.8 ppbv due to the increased emissions. The increase in averaged O3 in the CEC region resulting from the emission increase (4.0±1.9 ppbv) was higher than that caused by meteorological changes (3.1±4.9 ppbv) relative to the 2003 standard simulation, while the regions with larger O3 increases showed a higher sensitivity to meteorological conditions than to emission changes. Sensitivity tests indicate that increased levels of anthropogenic non-methane volatile organic compounds (NMVOCs) dominate the O3 increase over the eastern part of CEC, and anthropogenic nitrogen oxides (NOx) mainly increase MDA8 O3 over the central and western parts and decrease O3 in a few urban areas in the eastern part. Budget analysis showed that net photochemical production and meteorological conditions (transport in particular) are two important factors that influence O3 levels over the CEC. The results of this study suggest a need to further assess the effectiveness of control strategies for O3 pollution in the context of regional meteorology and anthropogenic emission changes.

Amides, a class of nitrogen-containing organic pollutants in the atmosphere, may affect the formation of atmospheric aerosols by the interactions with sulfuric acid. Here, the molecular interactions of sulfuric acid with formamide, methylformamide, dimethylformamide, acetamide, methylacetamide and dimethylacetamide was investigated by density functional theory. Geometry optimization and Gibbs free energy calculation were carried out at M06-2X/6-311++G(3df,3pd) level. The results indicate that the addition of amides to H2SO4 might have a promoting effect on atmospheric new particle formation at 298.15 K and 1 atm. In the initial stage of new particle formation, the binding capacity of amides and sulfuric acid is stronger than ammonia, but weaker than methylamine. It is worth noting that the trans-methylacetamide could have similar capabilities of stabilizing sulfuric acid as dimethylamine. In the presence of water, amides are found to only have a weak enhancement capability on new particle formation. In addition, we can infer from evaporation rate that the small molecule clusters of formamide and sulfuric acid may be more energetically favorable than macromolecule clusters.

Suffered from rapid recombination of electrons and holes, apparent photocatalytic activity (APA) of all photocatalysts can never achieve their theoretical ultimate values. But the upper limit of practical APA is of great significance to evaluate the practical application potential of a photocatalyst. Thus, in this work, the concept of ultimate apparent photocatalytic activity (UAPA) was firstly proposed and a convenient evaluation method was first established based on the nature that EDTA-2Na can exclusively scavenge photo-excited holes, and methyl orange (MO) is mainly attacked by superoxide radical (O2-) which is produced instantly by photo-excited electrons. From a macro perspective, six popular photocatalysts were designedly selected to verify the feasibility and application scope of the proposed UAPA evaluation method. Moreover, O2- production rate and photocurrent intensity were measured by spectroscopy and spectrum analyses, and theoretical carrier concentrations were calculated by density functional theory (DFT) to further confirm the rationality and reliability of the proposed method. Positive responses of all the tests guarantee that the proposed UAPA could precisely evaluate the application potential of a photocatalyst and rank the photocatalysts according to their practical potential.

Criegee intermediates (CIs) are short-lived carbonyl oxides, which can affect the budget of OH radicals, ozone, ammonia, organic/inorganic acids in the troposphere. This study investigated the reaction of CIs with serine (Ser) in the gas phase by using density functional theory (DFT) calculations and at the gas-liquid interface by using Born-Oppenheimer molecular dynamics (BOMD). The results reveal that the reactivity of the three functional groups of Ser can be ordered as follows: COOH > NH2 > OH. Water-mediated reactions of CIs with NH2 and OH groups of Ser on the droplet follow the proton exchange mechanism. The products, sulfuric acids, ammonia, and water molecules form stable clusters within 20 ns. This study shows that hydroperoxide products can contribute to new particle formation (NPF). The result deepens the understanding of the reaction of CIs with multifunctional pollutants and atmospheric behavior of CIs in polluted areas.

In recent years, highly oxygenated organic molecules (HOMs) derived from photochemical reactions of α-pinene, the most abundant monoterpene, have been considered as important precursors of biogenic particles. However, the specific reactions of HOMs remain largely unknown, especially the corresponding formation and nucleation mechanism in the nanoscale. In this study, we implemented quantum chemical calculations and molecular dynamics (MD) simulations to explore the mechanism of the formation of HOM monomers/dimers by ozonolysis and autoxidation of α-pinene. Furthermore, we investigated the mechanisms of HOMs with different oxygen-to‑carbon (O/C) ratios and functional groups participating in neutral and ion-induced nucleation. The results show that the formation of HOMs is hardly affected by water, sulfuric acid and ions. In the ion-induced nucleation, HOM can dominate the initial nucleation steps; however, in the neutral nucleation, HOMs are more likely to participate in the growth stage. In addition, the nucleation ability of HOM has a bearing on the O/C ratio and the types of the functional groups. The current calculations provide valuable insight into the formation mechanism of the pure organic particles at low sulfuric acid concentrations.

Novel waste-derived sorbents synthesized through one-step co-pyrolysis of wood and PVC (or brominated flame retarded plastic) were demonstrated as cost-effective sorbents for mercury (Hg) removal in our previous studies. To introduce magnetism and improve porosity, Fe species were further doped into such waste-derived sorbents. The ultimate fate of Hg-laden sorbents after their service is mainly disposed in landfill. Therefore, the stability of Hg/halogens on the spent sorbents is an important topic. In this work, the leachability of Hg/Cl/Br from four waste-derived sorbents was evaluated using toxicity characteristic leaching procedure (TCLP). Three traditional sorbents (Cl-impregnated activated carbon, Br-impregnated activated carbon and commercial activated carbon) were also tested for comparison. Experimental results suggested that the stability of Hg/Cl/Br on four waste-derived sorbents was far higher than that prepared by chemical impregnation. For four waste-derived sorbents, little Hg was leached out whereas certain amounts of Cl/Br escaped into the leachate. Interestingly, Fe-doping effectively improved the stability of Hg/Cl/Br on the waste-derived sorbents. Kinetic analysis revealed that diffusion process and surface chemical reaction were respectively the rate-limiting step for waste-derived sorbents before and after Fe-doping. Water-washing pretreatment could remove loosely-bonded Cl/Br from the waste-derived sorbents, while the Cl/Br essential for Hg removal was retained.

Cytochrome P450 enzymes (CYPs) are crucial for metabolizing dioxin compounds such as 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD). Here we have applied molecular dynamic simulations (MD), quantum mechanics/molecular mechanics methods (QM/MM) and density functional theory (DFT) to investigate the metabolic activation and transformation of PeCDD catalyzed by CYP1A1. Our QM/MM calculations highlight that PeCDD can be activated by P450s through the well-known electrophilic addition mechanism with an average energy barrier of 20.9 kcal/mol. Based on the results of previous experimental studies, further conversions of ketone products and epoxidation products that are mediated by P450 enzymes were investigated through DFT calculations. Analysis of the structures via the noncovalent interactions (NCI) method and the distortion-interaction model suggests that amino acids Ser122, Ala317, Ile386 and Leu496 play important roles in the metabolic process.

Chrysene, a four-ring polycyclic aromatic hydrocarbon (PAH), is recalcitrant to biodegradation and persistent in the environment due to its low water solubility. Here, we investigated the atmospheric degradation process of chrysene initiated by OH radical in the presence of O2 and NOX using quantum chemical calculations. The reaction mechanisms were elucidated by density functional theory (DFT) at M06–2X/6–311++G(3df,2p)//M06–2X/6-311+G(d,p) level, and the kinetics calculations were conducted with Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results show that the oxidation products of atmospheric chrysene are oxygenated PAHs (OPAHs) and nitro-PAHs (NPAHs), including nitro-chrysene, hydroxychrysene, hydroxychrysenone, 11-benzo[a]fluorenone and dialdehydes. Most of the products have deleterious effects on the environment and human beings due to their acute toxicity, carcinogenicity and mutagenicity. The overall rate constant for the reaction of chrysene with OH radical is 4.48 × 10−11 cm3 molecule−1 s−1 and the atmospheric lifetime of chrysene determined by OH radical is 6.4 h. The present work provided a comprehensive understanding on the degradation mechanisms and kinetics of chrysene, which could help to clarify its atmospheric fate and environmental risks.

Nitrous acid (HONO) is an important reservoir of the hydroxyl radical (OH) and thus plays a central role in tropospheric chemistry. Exhaust from engines has long been known as a major primary source of HONO, yet most previous studies focused on vehicle emissions on land. In comparison, ship emissions of HONO have been rarely characterized, and their impacts on the tropospheric oxidation chemistry have not been quantified. In this study, we conducted cruise measurements of HONO and related species over the East China Sea. Contrasting air masses from pristine marine background air to highly polluted ship plumes were encountered. The emission ratio of ΔHONO/ΔNOx (0.51 ± 0.18%) was derived from a large number of fresh ship plumes. Using the in-situ measured emission ratio, a global ship emission inventory of HONO was developed based on the international shipping emissions of NOx in the Community Emission Data System inventory. The global shipping voyage emits approximately 63.9 ± 22.2 Gg yr−1 of HONO to the atmosphere. GEOS-Chem modelling with the addition of ship-emitted HONO showed that HONO concentrations could increase up to 40–100% over the navigation areas, leading to about 5–15% increases of primary OH production in the early-morning time. This study elucidates the potentially considerable effects of ship HONO emissions on the marine atmospheric chemistry, and calls for further studies to better characterize the ship emissions of HONO and other reactive species, which should be taken into account by global and regional models.

Dehalogenation is one of the most important reactions in environmental pollution control, for instance, the degradation of persistent organic pollutants (POPs). Recently, fluoroacetate dehalogenase (FAcD) has been reported to catalyze the dehalogenation reactions, which shows great potential in treating halogenated pollutants. Here the dehalogenation mechanism catalyzed by FAcD was fully deciphered with the aid of quantum mechanics/molecular mechanics method. The results show that FAcD catalyzed dehalogenation efficiency follows the order of defluorination > dechlorination > debromination. The corresponding Boltzmann-weighted average barriers are 10.1, 19.7, and 20.9 kcal mol−1. Positive/negative correlations between activation barriers and structural parameters (e.g. distance and angle) for FAcD catalyzed dechlorination and debromination were established. Based on the structure-energy relationship, we propose that mutation of the binding pocket amino acids (e.g. His155, Trp156, Tyr219) to smaller proton donor amino acids (e.g. Serine, Threonine, Cysteine, Asparagine) may increase the efficiency for dechlorination and debromination. The results may of practical value for the efficient degradation of chlorined and bromined pollutants by harnessing FAcD.

The trends and mechanisms of organic carbon changes in coastal delta croplands are not yet clear due to the complexity physicochemical processes in soil. In this study, combing powder x-ray diffraction (XRD), microbial analysis, and density functional theory in quantum mechanics, we proposed a novel mechanism underlying OC accumulation. We investigated changes of three kinds of organic carbon (OC)-dissolved organic carbon (DOC), light fraction organic carbon (LFOC), and heavy fraction organic carbon (HFOC) in the Yellow River Delta croplands. We found that HFOC, dominant in coastal delta cropland soil, formed at different ages and its density increased with increasing reclamation time. Yet, DOC and LFOC had no significant increase or decrease tendency. Moreover, in coastal delta croplands, HFOC accumulation might be a complex progress, including the loss of indigenous OC and the accumulation of newly input OC. Based on these results, we proposed that although root exudative DOC (organic acids) could cause the indigenous OC loss by forming a specific microbial community, it still was a source of HFOC and promoted the OC accumulation. More importantly, based on density functional theory, we verified that these root exudative organic acids could adsorb on SiO2 together with crystalline Fe oxides (Fec) to form aggregates. The finding could explain the phenomenon that the XRD results showed samples were compounds of SiO2, Fec, and OC and the accumulation of HFOC in coastal delta croplands. By revealing a new OC accumulation mechanism in coastal delta croplands, this study provides novel insights into the mechanism of OC dynamics in coastal delta croplands and the global carbon budget.

Criegee intermediates (CIs), formed in the ozonolysis process of unsaturated hydrocarbons, play an important role in the formation of OH radicals, sulfuric acid, and aerosols. In this study, quantum chemical calculations were carried out to investigate the mechanism for the reaction of Criegee intermediates [involving CH2OO, CH3CHOO and (CH3)2COO] with OH radicals at the level of CCSD(T)/jun-cc-pVTZ//M06-2X/6-311 + G(2d,2p). A third component, such as water, ammonia, or amines, was introduced to the reaction of CIs with OH to evaluate their catalytic effect. The results show that the OH addition is the favorable channel among four channels involving cis-H abstraction, trans-H abstraction and O abstraction. The third component has a positively catalytic effect on the trans-H abstraction and O abstraction pathways. Moreover, for the trans-H abstraction of CH3CHOO and (CH3)2COO with OH, ammonia and amine exhibit more effectively catalytic ability than water. Furthermore, Born-Oppenheimer molecular dynamic simulation results show that the addition of third component to CIs and hydrogen abstraction from the third component by OH occur simultaneously.

Isoprene is the most abundant non-methane VOC and a significant SOA contributor. The atmospheric oxidation initiated by atomic chlorine is an important sink for isoprene, especially in certain regions with high Cl concentration, while its detailed oxidation mechanism remains unclear. In this work, we comprehensively investigated the reaction mechanism of isoprene with Cl using quantum chemistry calculation, and first elaborated the specific reaction mechanisms of chloroalkenyl peroxy radicals with HO2/NO and the formation of 2-methylbut-3-enal, highlighting their important roles in the SOA formation. For the initial reactions, Cl additions to terminal carbons and H abstraction from CH3 moiety of isoprene are the predominant reactions, which is consistent with previous research. Following the initial reactions, their subsequent reactions with O2 and HO2 (or NO) under different atmospheric conditions could lead to the formation of 17 highly oxidized molecules (HOMs), of which P10, P12, P16, P17, P19 and P33 generated by the subsequent reactions of the major first-generation products (MVK, CMBO, CMBA and MBO) have been detected in the reaction process of isoprene with Cl in the chamber experiment. In addition to auto-oxidation process, the reaction of chloroalkenyl peroxy radicals with HO2/NO and their subsequent reactions are all easy to occur under atmospheric conditions, which could be crucial contributors to the formation of HOMs and SOA arising from the Cl initiated oxidation of isoprene. This study would be conducive to clarifying the atmospheric oxidation process of isoprene initiated by Cl and providing a new understanding of its SOA formation.

Polycyclic aromatic hydrocarbons (PAHs) are highly toxic, mutagenic and/or carcinogenic to humans. To reduce the emission of PAHs, it's significant and indispensable to explore the PAH formation mechanism. In the present work, the growth mechanism of PAHs from the reactions of anthracene and phenanthrene with cyclopentadienyl and indenyl radicals was investigated with the aid of high-accuracy quantum chemistry calculation. The rate constants of key elementary steps were calculated by meaning of the canonical variation transition-state (CVT) theory with the small curvature tunneling (SCT) correction over the temperature range of 400–1400 K. The mechanism of the PAH formation involves in six elementary steps, addition reaction, ring closure, intramolecular H-shift, cleavage of C C bond, intramolecular H-shift and unimolecular elimination of CH 3 or H. The cleavage of C C bond is the rate-determining step due to the high barrier. The formation of PAHs from the reactions of anthracene with cyclopentadienyl and indenyl radicals is easier than that from the reactions of phenanthrene.

Elucidating the metabolic mechanism and the derivatives of polybrominated diphenyl ethers (PBDEs) is significant to risk assessment. This study delineated the metabolic mechanism of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) catalyzed by P450 enzymes using a combination of molecular dynamic (MD), quantum mechanics/molecular mechanics (QM/MM) and density functional theory (DFT). The calculation results reveal that the electrophilic addition is the main pathway for the biotransformation of BDE-47 catalyzed by P450 enzymes. 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE-47) is a more kinetically preferable product than 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (5-OH-BDE-47). Electrophilic addition reaction can lead to the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). The ecotoxicity assessment indicates that the final products of BDE-47 are still toxic to aquatic organisms, but the solubility increase of the hydroxylated products can accelerate their excretion from the body. We expect that the established metabolic mechanism and the derivatives will be used to predict the biotransformation of other PBDE congeners catalyzed by P450 enzymes in human livers.

Ground-level ozone (O3) has become the principal air pollutant in Beijing during recent summers. In this context, an investigation of ambient concentrations and variation characteristics of O3 and its precursors in May and June from 2014 to 2017 in a typical urban area of Beijing was carried out, and the formation sensitivity and different causes of heavy O3 pollution (HOP, daily maximum 8-h O3 (MDA8h O3)>124 ppbv) were analyzed. The results showed that the monthly assessment values of the O3 concentrations (the 90th percentile MDA8h O3 within one month) were highest in May or June from 2014 to 2017, and the values presented an overall increasing trend. During this period, the number of O3 pollution days (MDA8h O3 > 75 ppbv) also showed an increasing trend. During the HOP episodes, the concentrations of volatile organic compounds (VOCs), nitrogen oxides (NOX), and carbon monoxide (CO) were higher than their respective mean values in May and June, and the meteorological conditions were more conducive to atmospheric photochemical reactions. The HOP episodes were mainly caused by local photochemical formation. From 2014 to 2017, O3 formation during the HOP episodes shifted from VOC and NOX mixed-limited to VOC-limited conditions, and O3 formation was most sensitive to anthropogenic VOCs. Six categories of VOC sources were identified, among which vehicular exhaust contributed the most to anthropogenic VOCs. The VOC concentrations and OFPs of anthropogenic sources have decreased significantly in recent years, indicating that VOC control measures have been effective in Beijing. Nevertheless, NOX concentrations did not show an evident decreasing trend in the same period. Therefore, more attention should be devoted to O3 pollution control in May and June; control measure adjustments are needed according to the changes in O3 precursors, and coordinated control of VOCs and NOX should be strengthened in long-term planning.

Predicting the detoxifying mechanism and potential toxic derivatives of xenobiotic substances is significant for risk assessment. The present study delineated the detoxifying mechanism of 1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene (DDT) metabolized by human P450 enzymes using a combination of molecular dynamic (MD), quantum mechanics/molecular mechanics (QM/MM) and density functional theory (DFT). This study highlights that DDT can be metabolized by P450 enzymes through the hydrogen abstraction and electrophilic addition mechanism, and the main derivatives are epoxides (2,3-oxide-DDT and 3,4-oxide-DDT), DDE and dicofol. The epoxides are unstable and the C-O bond cleavage easily occurs by the reaction with hydronium ion or hydroxyl radicals, yielding endocrine disruptor hydroxylated DDT. The eco-toxicity evaluation indicates that the derivatives of DDT are less toxic than DDT, and the solubility increase of the derivatives can accelerate their excretion from the body. The study can provide an understanding of the biotransformation of DDT by the P450 enzymes in human livers.

Cytochrome P450 enzymes (CYPs) play an essential role in the bio-transformation of polychlorinated biphenyls (PCBs). The present work implemented quantum mechanic/molecular mechanic methods (QM/MM) and density functional theory (DFT) to study the metabolic activation of 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB136) catalyzed by CYP2B6. Electrophilic additions at the Cα and Cβ positions generate different active intermediates. The electrophilic addition energy barrier of Cβ is 10.9 kcal/mol higher than that of Cα, and Cα is the preferred site for the electrophilic addition reaction. Based on the previous experimental studies, this work investigated the mechanism of converting active intermediates into OH-PCB136, which has high toxicity in a non-enzymatic environment. Structural analysis via the electrostatic and noncovalent interactions indicates that Phe108, Ile114, Phe115, Phe206, Phe297, Ala298, Leu363, Val367, TIP32475 and TIP32667 play crucial roles in substrate recognition and metabolism. The analysis suggests that the halogen-π interactions are important factors for the metabolism of CYP2B6 to halogenated environmental pollutants. This work improved the understanding of the metabolism and activation process of chiral PCBs, and can be used as a guide to improve the microbial degradation efficiency of PCB136.

A magnetic amine-crosslinked reed (MACR) was synthesized by an insitu precipitation method and used for perchlorate uptake. The morphological properties of clean MACR, perchlorate-saturated MACR and bio-regenerated MACR samples were determined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. The adsorption capacities of perchlorate by clean and bio-regenerated MACRs were determined. The density functional theory (DFT) method was employed to evaluate the binding free energies between various anions and ammonium/hydroxy groups. The maximum adsorption (Q max ) of perchlorate by MACR was calculated to be 195.5–232.8 mg/g at 30–50 °C. The theoretical computation of adsorption-free energies indicated that ammonium groups were dominant in the process of perchlorate adsorption; other anions, such as [H 2 PO 4 ] - , [NO 3 ] - and [SO 4 ] 2- , showed relatively higher binding free energies than [ClO 4 ] - , which corresponded to the results of competitive adsorption. The spent MACR was then bio-regenerated in a sealed 250-ml conical flask with perchlorate-reducing bacteria (30 °C, 160 rpm) and reached 81.4% of recovery within 3 days. Some hydrophobic macromolecules of extracellular polymeric substances (EPS) might have attached to the surface of MACR, which was validated by the zeta potential, SEM and excitation emission matrix (EEM) fluorescence spectroscopy results.

The reactions of Criegee intermediates with trace gases (such as alcohols, amines, and acids) are primarily dependent on the trace gases' functional group activity. In this study, we used density functional theory calculations and ab initio dynamics simulation methods to explore the synergistic effect of NH2 and OH groups, in the multifunctional compound monoethanolamine (MEA), on the Criegee reaction. The results showed that among the four evaluated MEA configurations, two functional groups in the g′Gg′ and tGg′ configurations, -NH2 and -OH, have the synergistic effect on the C2 stabilized Criegee intermediates (sCIs). At the gas-liquid interface, sCIs react with NH2 groups of MEA molecules directly or are mediated by water molecules, resulting in additional product formation. The rate calculation indicated that the reaction of sCIs with NH2 groups of MEA molecules is prior to that with OH groups. In addition, OH groups promote the reactions between sCIs and NH2 groups of MEA, while the presence of NH2 groups weakens the reactions of sCIs and OH groups of MEA to some extent. At 298 K, the total rate constant of anti-CH3CHOO with NH2 group of MEA is 4.26 × 10−11 cm3 molecule−1 s−1, which is four orders of magnitude higher than that of anti-CH3CHOO hydration. Under low humidity conditions, the reactions between sCIs and MEA could contribute to the removal of sCIs.

The danger of zearalenone (ZEN) as an endocrine disruptor to humans and the environment has aroused increasing attention. In this study, we implemented the quantum mechanics/molecular mechanics (QM/MM) method to investigate the degradation mechanism of ZEN hydrolase (RmZHD) toward ZEN at the atomic level. The degradation process involves two concerted reaction pathways, where the active site contains a Ser-His-Glu triplet as a proton donor. With the Boltzmann-weighted average potential barriers of 18.1 and 21.5 kcal/mol, the process undergoes proton transfer and nucleophilic-substituted ring opening to form a hydroxyl product. Non-covalent interaction analyses elucidated hydrogen bonding between key amino acids with ZEN. The electrostatic influence analysis of 16 amino acids proposes residues Asp34 and His128 as the possible mutation target for future mutation design of enzyme RmZHD. An in-depth investigation of the protein environment of RmZHD can improve the bioremediation efficiency of endocrine disrupting chemicals.

Biphenyl 2,3-dioxygenase (BphA), a Rieske-type and first enzyme in the aerobic degradation process, plays a key role in the metabolizing process of biphenyl/polychlorinated biphenyl aromatic pollutants in the environment. To understand the catalytic mechanism of biphenyl 2,3-dioxygenase, the conversions leading to the cis-diols are investigated by means of quantum mechanics/molecular mechanics (QM/MM) method. A hydroperoxo-iron (III) species is involved in the enzyme-catalyzed reaction. Herein, we explored the direct reaction mechanism of hydroperoxo-iron (III) species with biphenyl and 4-4'-dichlorobiphenyl. The reaction process involves an epoxide intermediate, it could develop into a carbocation intermediate, and ultimately evolve into a cis-diol product. The important roles of several residues during the dioxygenation process were highlighted. This study may provide theoretical support for further directed mutations and enzymatic engineering of BphA, as well as promote the development of degrading environmentally persistent biphenyl/polychlorinated biphenyl aromatic contaminants.

In recent years, Criegee chemistry has become an important research focus due to its relevance in regulating concentrations of tropospheric OH radicals, hydroperoxides, sulfates, nitrates, and aerosols. However, to date, its interface behavior remains poorly understood. Thus, in this study, we used the Born-Oppenheimer molecular dynamics (BOMD) simulation method to explore the reaction mechanisms between Criegee intermediates (CIs) and methylsulfonic acid (MSA) at the air-water interface, then compared the observed behaviors with those in the gas phase. The addition of Criegee intermediates to MSA is nearly a barrierless reaction and follows a loop-structure mechanism in the gas phase. The high rate constants indicate that the Criegee intermediates and MSA reactions are the main acid removal channels. At the water's surface, the interaction of Criegee intermediates with MSA includes three main channels: 1) direct addition reaction, 2) H2O-mediated hydroperoxide formation, and 3) MSA-mediated Criegee hydration. These reaction channels follow a loop-structure or a stepwise mechanism and proceed at the picosecond time-scale. The results of this work broaden our understanding of Criegee atmospheric behaviors in polluted urban and marine areas, which in turn will aid in developing more effective pollution control measures.

Nitrated phenols are receiving increasing attention due to their adverse impacts on the environment and human health. Previous measurements have revealed the non-ignorable contribution of vehicle exhaust to atmospheric nitrated phenols in urban areas. However, there is a lack of comprehensive understanding of the emission characteristics and the total emission of nitrated phenols from current on-road traffic. This study investigated the emissions from eight passenger vehicles, eight trucks, and two taxis, with fuel types including diesel, gasoline, and compressed natural gas. Exhaust emissions were collected and measured using a mobile measurement system on two testing routes. Twelve nitrated phenols in the collected fine particulate matter were detected using ultrahigh performance liquid chromatography-mass spectrometry. Overall, the emission profiles of fine particulate nitrated phenols varied with vehicle load and fuel type. The 4-nitrophenol and its methyl derivatives were dominant nitrated phenol species emitted by the vehicles with proportions of 38.4%–68.0%, which is significantly different from the proportions of nitrated phenols emitted from biomass burning and coal combustion. The emission factors also exhibited large variations across vehicle type, fuel type, and emission standards, with relatively low values for gasoline vehicles and taxis fueled by compressed natural gas and high values for diesel vehicles. Based on the emission factors of nitrated phenols from different vehicles, the estimated total emission of nitrated phenols from on-road vehicles in China was 58.9 Mg (−86%–85% within 95% confidence interval), with diesel trucks contributing the most substantial fractions. This work highlights the very high level of emissions of nitrated phenols from diesel vehicles and provides an essential basis for atmospheric modeling and effective pollution control.

cis-Pinonic acid (CPA), one of the major photooxidation products of α-pinene, is believed to contribute to the formation of aerosols formed over forested areas. In the current study, we implement quantum chemical calculation to investigate the interaction between sulfuric acid (SA) and CPA as well as the hydrolysate of CPA (HCPA) in the presence of water or ammonia in the atmosphere. The lowest free energy configurations, reactants, transition states, intermediates, and products were optimized at 298/278 K and 1 atm at the M06-2X/6-311+G(3df,3pd) level. Our results show that one CPA molecule might initially nucleate with SA molecules and subsequently participate in the formation and growth of the new particle in the form of HCPA. More than one HCPA molecule may be involved in the critical nuclei. Furthermore, the hydrolysis reaction of CPA can be effectively catalyzed by SA and nitric acid (NA) in presence of water, which significantly increases the HCPA content in the atmosphere and subsequently promotes the particle nucleation. Overall, the current study elucidates a new mechanism of atmospheric nucleation driven by CPA and its hydrolysate.

Atmospheric oxidation of fluorene and its derivatives initiated by OH radicals was investigated theoretically with quantum chemical calculation methods [M06-2X/6-311++G(3df,2p)//M06-2X/6-311+G(d,p)]. It revealed that the OH addition pathways form hydroxyfluorene and ring-opening product dialdehyde while the H abstraction pathways lead to the formation of 9-fluorenone. Subsequent oxidation of 9-fluorenone has considerable potential to form dibenzo-p-dioxin and nitrofluorenone according to the present calculation results. The atmospheric lifetime of fluorene relative to the reactions with OH radicals is deduced to be 12.51 h based on the calculated overall rate constant (2.29 × 10−11 cm3 molecule−1 s−1) at 298 K and 1 atm. The oxidation products of fluorene in the atmosphere are generally more toxic and persistent. This work provides a comprehensive explanation for atmospheric oxidation processes of fluorene and facilitates clarifying its environmental risks.

International audience; Bacteria are ubiquitous in the near-surface atmosphere where they constitute an important component of aerosols with the potential to affect climate change, ecosystems, atmospheric process and human health. Limitation in tracking bacterial diversity accurately has thus far prevented the knowledge of airborne bacteria and their pathogenic properties. We performed a comprehensive assessment of bacterial abundance and diverse community in PM2.5 collected at Mt. Tai, via high-throughput sequencing and real-time PCR. The samples exhibited a high microbial biodiversity and complex chemical composition. The dominating populations were gram-negative bacteria including Burkholderia, Delftia, Bradyrhizobium, and Methylobacterium. The PM mass concentration, chemical composition, bacterial concentration and community structure varied under the influence of different air-mass trajectories. The highest mass concentration of PM2.5 (61 μg m-3) and major chemical components were recorded during periods when marine southeasterly air masses were dominant. The local terrestrial air masses from Shandong peninsula and its adjacent areas harbored highest bacterial concentration loading (602 cells m-3) and more potential pathogens at the site. In contrast, samples influenced by the long-distance air flow from Siberia and Outer Mongolia were found to have a highest richness and diversity as an average, which was also marked by the increase of dust-associated bacteria (Brevibacillus and Staphylococcus). The primary research may serve as an important reference for the environmental microbiologist, health workers, and city planners.

Polychlorinated dibenzo‑p‑dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are highly toxic, carcinogenic and mutagenic to humans. As precursors of PCDD/Fs, dibenzofuran (DF) and dibenzo‑p‑dioxin (DD) have received considerable public and scientific attention. To reduce the emission of PCDD/Fs, it is critical to explore the formation mechanisms of DF and DD. The present study delineated the DF and DD formation mechanisms from anthracene partial oxidation with the aid of high-accuracy quantum chemistry calculations. The rate constants of crucial elementary steps were obtained utilizing canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction. The results indicate that anthracene could be important precursor of DF and DD, because of the potential barriers for all the major elementary reactions are lower than 33.54kcalmol-1. This work also reveals that water molecule plays an important catalytic effect during the formation of both DF and DD by lowering the barriers of about 27.24kcalmol-1. For the water-assisted formation pathway, DF is the dominate product of anthracene partial oxidation with the highest barrier of 30.45kcalmol-1. For the non-water-assisted formation pathway, DD is the dominate product with the highest barrier of 33.54kcalmol-1.

International audience; Aiming to a better understanding sources contributions and regional sources of fine particles, a total of 273 filter samples (159 of PM2.5 and 114 of PM1.0) were collected per 8 h during the winter 2016 at a southwest suburb of Beijing. Chemical compositions, including water soluble ions, organic carbon (OC), and elemental carbon (EC), as well as secondary organic carbon (SOC), were systematically analyzed and estimated. The total ions concentrations (TIC), OC, and SOC of PM2.5 were with the following order: 16:00–24:00 > 08:00–16:00 > 00:00–08:00. Since primary OC and EC were mainly attributed to the residential combustion in the night time, their valley values were observed in the daytime (08:00–16:00). However, the highest ratio value of SOC/OC was observed in the daytime. It is because that SOC is easily formed under sunshine and relatively high temperature in the daytime. Positive matrix factorization (PMF), clustering, and potential source contribution function (PSCF) were employed for apportioning sources contributions and speculating potential sources spatial distributions. The average concentrations of each species and the source contributions to each species were calculated based on the data of species concentrations with an 8 h period simulated by PMF model. Six likely sources, including secondary inorganic aerosols, coal combustion, industrial and traffic emissions, road dust, soil and construction dust, and biomass burning, were contributed to PM2.5 accounting for 29%, 21%, 17%, 16%, 9%, 8%, respectively. The results of cluster analysis indicated that most of air masses were transported from West and Northwest directions to the sampling location during the observation campaign. Several seriously polluted areas that might affect the air quality of Beijing by long-range transport were identified. Most of air masses were transported from Western and Northwestern China. According to the results of PSCF analysis, Western Shandong, Southern Hebei, Northern Henan, Western Inner Mongolia, Northern Shaanxi, and the whole Shanxi provinces should be the key areas of air pollution control in China. The exposure-response function was used to estimate the health impact associated with PM2.5 pollution. The population affected by PM2.5 during haze episodes reached 0.31 million, the premature death cases associated with PM2.5 reached 2032. These results provided important implication for making environmental policies to improve air quality in China.

Aromatic compounds (ACs) give a substantial contribution to the anthropogenic emissions of volatile organic compounds. Nitrate radicals ( NO3) are significant oxidants in the lower troposphere during nighttime, with concentrations of (2-20) × 108 molecules cm−3. In this study, the tropospheric gas and liquid phase reactions of ACs with nitrate radical are investigated using theoretical computational methods, which can give a deep insight into the reaction mechanisms and kinetics. Results show that the reactivity of ACs with nitrate radicals decreases as the electron donating characteristics of the functional group on the ACs decrease, as ΔG≠ of the reaction with NO3 increasing from -1.17 to 17.84 kcal mol-1. The reaction of NO3 towards ACs in the aqueous phase is more preferable, with the atmospheric lifetime 0.07–1281 min. An assessment of the aquatic toxicity of ACs and their degradation products indicated that the risk of their degradation products remains and should be given more attention.

Phenanthrene (Phe) is one of the most abundant polycyclic aromatic hydrocarbons (PAHs) observed in polluted urban atmosphere. The most important atmospheric loss process of Phe is the reaction with OH radicals. The present work investigated OH radical-initiated atmospheric degradation of Phe in the presence of O2 and NOx. The possible reaction mechanism was elucidated by density functional theory (DFT) calculations. Calculations show that the main products are a series of ring-retaining and ring-opening oxygenated PAHs containing phenanthrol, phenanthones, phenanthrenequinone, and dialdehydes. Rice-Ramsperger-Kassel-Marcus (RRKM) theory was employed to evaluate the rate constants for the initial steps of Phe with OH. The atmospheric lifetime of Phe relative to gas-phase reactions with OH is estimated to be 4.6h, based on the calculated overall rate constant of 3.02×10(-11)cm(3) molecule(-1)s(-1) at 298K and 1atm. Combined with available experimental data, this work also provides a comprehensive investigation of the formation mechanism of oxygenated PAHs in the atmospheric oxidation process of phenanthrene and should help to clarify its potential health risk.

Nitrated polycyclic aromatic hydrocarbons have received an increasing number of considerations because of their higher mutagens than parent PAHs. In this paper, the formation of dinitro-naphthalene was investigated mechanistically using 1- and 2-nitronaphthalene as precursors with the aid of high-accuracy quantum chemistry calculation. The geometrical parameters, as well as vibrational frequencies, were calculated at the BB1K/6-31+G(d,p) level. Water molecule plays an important role in the formation of dinitro-naphthalene. The rate constants were deduced by canonical variational transition-state theory with small curvature tunneling contribution over the temperature range of 273-333 K. Meanwhile, the Arrhenius formulas were fitted for the OH addition of both 1- and 2-nitronaphthalene. The calculated overall rate constants for 1-nitronaphthalene and 2-nitronaphthalene at 298 K and 1 atm are 7.43 × 10(-13) and 7.48 × 10(-13) cm(3) molecule(-1) s(-1), respectively. The rate constants of NO3 addition to 1-nitronaphthalene and 2-nitronaphthalene by RRKM method at 298 K and 1 atm are 3.55 × 10(-15) and 3.47 × 10(-15) cm(3) molecule(-1) s(-1), respectively. This study provides a comprehensive investigation of the formation process of dinitro-naphthalenes, initiated by OH and NO3 radicals and should facilitate to illuminate its atmospheric source. Oxygen may probably be competitive with the second NO2 addition step when the concentration of NO2 is at low level.

Characteristics and transformation of nitrous acid (HONO) and particulate nitrite were investigated with high time-resolution field measurements at an urban site in Ji'nan, China from Nov. 2013 to Jan. 2014. During the sampling period, averages of 0.35ppbv HONO and 2.08μgm(-3) fine particulate nitrite were observed. HONO and particulate nitrite exhibited similar diurnal variation patterns but differed in the time at which concentration peaks and valleys occurred. Elevated nocturnal HONO concentration peaks were mainly associated with primary emissions from vehicle exhaust and secondary formation via heterogeneous reactions of NO2. In fresh air masses dominated by vehicle emissions, the average HONO/NOx ratio was 0.58%. The nocturnal heterogeneous reactions of NO2 contributed to about half of the elevated HONO concentration peaks, with the conversion rates in the range of 0.05% to 0.96%h(-1). Meanwhile, a large amount of particulate nitrite, which greatly exceeded the concentration of the gas-phase HONO, was also produced through the heterogeneous reactions of NO2. The large yields of particulate nitrite were facilitated by abundant ammonia and particulate cations in urban Ji'nan. Notably, in the daytime, particulate nitrite acted as a potential source of HONO, especially in conditions of low humidity and acidic aerosols, which possibly has subsequent effects on photochemistry in the boundary layer.

The atmospheric degradation of polycyclic aromatic hydrocarbons (PAHs) can generate organic pollutants that contribute to the formation of secondary organic aerosols (SOAs) and exacerbate their carcinogenicity. Indene is an example of styrene-like bicyclic hydrocarbons that are not fully aromatic. The OH-initiated atmospheric oxidation of indene in the presence of O2 and NO was investigated using quantum chemical methods at M06–2X/6–311++G(3df,2p)//M06–2X/6-311+G(d,p) level. The oxidation products are oxygenated polycyclic aromatic hydrocarbons (OPAHs) containing hydroxyindene, indenone, dialdehydes and 2-(formylmethyl)benzaldehyde. Calculation results showed that 7-indene radical, which is the precursor of various PAHs, has a high production ratio that is 35.29% in the initial reaction, indicating that the OH-initiated oxidation increase the environmental risks of indene in the atmosphere. The rate constants for the crucial elementary reactions were calculated based on Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The overall rate constant of the initial reaction is calculated to be 1.04 × 10−10 cm3 molecule−1 s−1 and the atmospheric lifetime of indene is determined as 2.74 h. This work provides a comprehensive understanding on the oxidation mechanisms of indene and the findings could help to clarify the fate of indene in the atmosphere.

New particle formation (NPF) involving amines in the atmosphere is considered an aggregation process, during which stable molecular clusters are formed from amines and sulfuric acid via hydrogen bond interaction. In this work, ab initio dynamics simulations of ammonium bisulfate formation from a series of amines, SO3, and H2O molecules were carried out in the gas phase and at the air-water interface. The results show that reactions between amines and hydrated SO3 molecules in the gas phase are barrierless or nearly barrierless processes. The reaction rate is related to the basicity of gas-phase amines—the stronger the basicity, the faster the reaction. Furthermore, SO3 hydrolysis catalyzed by amines occurs simultaneously with H2SO4-amine cluster formation. At the air-water interface, reactions between amines and SO3 involve multiple water molecules. The reaction center’s ring structure (amine–SO3–nH2O) promotes the transfer of protons in the water molecules. The formed ammonium cation (-RNH3+) and the bisulfate anion (HSO4−) are present and stable by means of hydrogen bond interaction. The cluster formation mechanism provides new insights into NPF involving amines, which may play an important role in the formation of aerosols in some heavily polluted areas — e.g., those with a high amine concentration.

Aerosol samples from all over the word contained 2-methyltetrol sulfate ester (MTS). We investigated the role of MTS in new particle formation (NPF) with aerosol nucleation precursors, including sulfuric acid (SA), water (W), ammonia (N), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA). The analysis was performed using quantum chemical approach, kinetic calculation and molecular dynamics (MD) simulations. The results proved that the molecular interactions in the clusters were mainly H-bonds and electrostatic interaction. The negative Gibbs free energy changes for all the studied MTS-containing clusters indicated that the formation of these clusters was thermodynamically favorable. The stability of the clusters was evaluated according to the total evaporation rate. Here, (MTS)(SA) and (MTS)(W) were the most and least stable cluster, respectively. MD simulations were used for time and spatial analysis of the role of the MTS-SA system. The results indicated that MTS can self-aggregate or absorb SA molecules into clusters, larger than the size of the critical cluster (approximately 1 nm), suggesting that MTS can initiate NPF by itself or together with SA.